Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T137/00—Fluid handling
  • Y10T137/0318—Processes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
  • Y10T428/1393—Multilayer [continuous layer]

Definitions

• the present invention relates to a use of a particular multilayer structure for the manufacture of gas pipes, and more particularly for methane pipes.
• the essential criterion is the barrier property of the gas hose conveyed as well as the criteria conventionally imposed by user specifications, such as cold shock, heat resistance, bond strength, salt resistance ( ZnCl) ...
• thermoplastic multilayer structures could very advantageously be used for the manufacture of gas pipes in place of the current elastomeric structures.
• thermoplastic multilayer structure for transporting gas.
• This structure comprises at least one layer consisting essentially of polyethylene (which is understood as homopolymer or copolymer of ethylene) and an outer layer of polyamide.
• the invention thus relates to the use of a multilayer structure for the manufacture of gas pipes, especially natural gas, this structure overcomes the disadvantages of elastomeric structures and thermoplastic structures taught by the document US 2002/036405, and having, among others and simultaneously, good barrier properties to the gas carried and heat resistance.
• the invention relates in particular to the use of a multilayer structure for the manufacture of methane pipes.
• this use implements a multilayer structure comprising, from outside to inside, the following successive layers, these layers adhering to their respective contact zone:
• a layer 1 comprising at least one polyamide, the polyamide being chosen from PA 11, PA 12 and an aliphatic polyamide resulting from the condensation of an aliphatic diamine having from 6 to 18 carbon atoms and an aliphatic diacid having from 9 to 18 carbon atoms,
• a layer 2 of binder optionally, a layer 2 of binder, and
• a layer 3 chosen from an EVOH layer, a layer formed from a mixture of polyamide and a polyolefin with a polyamide matrix, a layer of PA 6 or PA 6-6, a layer of semi-aromatic polyamide or of semi-aromatic copolyamide and a layer of polyphthalamide (PPA), the layer 3 being intended to be in contact with the gas carried.
• PPA polyphthalamide
• the structures used in the context of the use according to the present invention are highly gas barrier, such as methane.
• methane it is considered that one has good barrier properties when the permeability, measured at 23 ° C, is less than 5 cm 3 .mm / m 2 .24 h.atm.
• Such structures are in addition highly barrier while being able to involve only a limited number of layers.
• structures consisting of 2 layers or 3 layers, in the case where the presence of a binder layer would be necessary to ensure the adhesion of layers 1 and 3, are quite conceivable.
• the multilayer structures used do not comprise any layer made of polyethylene such as that described in document US 2002/036405.
• the multilayer structure used for the manufacture of the gas pipes is formed of two or three successive layers, the layer 1, the layer 2 which is optional and the layer 3, the layer 3 being intended to be in contact with the gas conveyed by the pipe.
• Layer 1 comprises at least one polyamide, the polyamide being chosen from PA 11, PA 12 and an aliphatic polyamide resulting from the condensation of an aliphatic diamine having 6 to 18 carbon atoms and an aliphatic diacid having 9 to 18 carbon atoms.
• PA 6-12, PA 9-12, PA 10-10 or PA 10-12 can be used in the composition of layer 1.
• the PA 11, the PA 12 or the aliphatic polyamide of the layer 1 may also comprise at least one additive chosen from plasticizers, impact modifiers, dyes, pigments, brighteners, antioxidants, UV stabilizers and polyolefins, the latter may be functionalized or not.
• BBSA n-butyl benzene sulfonamide
• the layer 2 is a layer of binder that allows the adhesion of the different layers together to avoid any delamination phenomenon.
• the layer 2 must adhere perfectly to the layers 1 and 3.
• the binder is conventionally a functionalized polyolefin, the functionalization of the polyolefin being provided by a carboxylic acid or an anhydride of carboxylic acid, grafted or copolymerized.
• This functionalized polyolefin may be mixed with an unfunctionalized polyolefin.
• the binder can also be a copolyamide or a mixture of copolyamides. Copolyamide compositions which are suitable for the multilayer structure according to the present invention are also described in US 2005/0031818 A1 (paragraphs [0094] to [0111]) and in US 7,063,873 (Col. 5, 1). 3 to 6, 1. 50).
• the binder may further comprise at least one additive chosen from plasticizers, impact modifiers, dyes, pigments, brighteners, antioxidants, UV stabilizers and polyolefins, the latter being able to be functionalized or not.
• the binder may comprise an impact modifier chosen from elastomers and very low density polyethylenes, this impact modifier being wholly or partly functionalized.
• WO 2006/066944 A1 which describes in a detailed manner shock modifiers suitable for the purposes of the present invention.
• This layer 2 is however optional. Indeed, for the sake of cost control, this layer 2 will not be interposed between layers 1 and 3, in the particular case where the compositions of layers 1 and 3 adhere well to each other. Layer 3
• the layer 3 is chosen from an EVOH layer, a layer formed from a mixture of polyamide and a polyolefin with polyamide matrix, a layer of PA 6 or PA 6-6, a layer of polyamide semiaromatic or of semi-aromatic copolyamide and a layer of polyphthalamide (PPA).
• the layer 3 may be an EVOH layer, the EVOH being a saponified ethylene-vinyl acetate copolymer.
• EVOH layer is meant both a layer consisting of EVOH, a layer formed of a mixture comprising at least 40% by weight of EVOH, the other constituents of the mixture then being chosen from polyolefins, polyamides and optionally functional polymers.
• EVOH-based compositions suitable for the multilayer structures used in the context of the present invention have in particular been described in document US Pat. No. 7,063,873 (Col. 7,18 to 8).
• the layer 3 may also be formed by a mixture of polyamide (A) and polyolefin (B) polyamide matrix.
• Polyamide (A) means the condensation products of: - one or more amino acids
• copolyamides such as those resulting from the condensation of: at least two alpha omega aminocarboxylic acids,
• At least one alpha omega aminocarboxylic acid at least one diamine and at least one diacid, or at least one lactam, at least one diamine and at least one diacid.
• the polyamide may be chosen from PA 6 and PA 6-6; the copolyamide may be chosen from PA 6/12, PA 6 / 6-6, PA 6/12 / 6-6, PA 6 / 6-9 / 11/12, PA 6 / 6-6 / 11/12 and PA 6-9 / 12. It is also possible to use mixtures of polyamides and / or copolyamides.
• polyolefin (B) is meant a functionalized polyolefin (B1), a non-functionalized polyolefin (B2) or a mixture of at least one functionalized polyolefin (B1) and / or at least one nonfunctionalized polyolefin (B2).
• An unfunctionalized polyolefin (B2) is conventionally a homopolymer or a copolymer of alpha olefins or diolefins.
• a functionalized polyolefin (B1) is generally a homopolymer or copolymer of alpha olefins having reactive units (functionalities), these reactive units being acid, anhydride or epoxy functions.
• Functionalized polyolefins (B1) and non-functionalized polyolefins (B2) suitable for a layer 3 composition comprising a polyamide (A) and a polyolefin (B) with a polyamide matrix are very widely described in document US 2005/0031818 A1, in which particularly in paragraphs [0124] to [0205].
• functionalized polyolefins include terpolymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate, such as Lotader ®, or polyolefins grafted with anhydride maleic, such as Orevac ® , these products being marketed by the Applicant.
• Layer 3 can also be PA 6 or PA 6-6.
• Layer 3 may be further a semi-aromatic polyamide or a semi-aromatic copolvamide.
• semi-aromatic polyamides have been described in particular in GB 1490453, US 2,766,221 and more recently in WO 2006/108721 A1.
• MXD.10 denotes the condensation product of a mixture of xylylenediamines containing 70 to 100% metaxylylenediamine and sebacic acid
• Z denotes at least one unit chosen from:
• Y1 denotes the residues of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid, the weight ratio Z / (MXD + 10 + Z) being between 0 and 15%.
• the semi-aromatic copolyamide corresponds to the general formula X / Y, Ar in which:
• Y represents the residues of an aliphatic diamine having from 6 to 20 carbon atoms
• Ar denotes the residues of an aromatic dicarboxylic acid
• X denotes: either the residues of the aminoundecanoic acid NH2- (CH2) ifj '
• the following semiaromatic copolyamides may be mentioned without limitation: 6.6 / 6, T; 6/6, T; 6, I / 6, T; 12/6, T; 12.12 / 12, T; 10.6 / 10, T; 11/10, T;
• the layer 3 may be a layer of poly (phthalamide) (PPA).
• PPA is an aromatic polyamide obtained by the polycondensation of at least one phthalic acid and at least one aliphatic diamine.
• the phthalic acid may be a terephthalic, isophthalic or orthophthalic acid or a mixture comprising at least two of said acids.
• the aliphatic diamine advantageously comprises from 3 to 12 carbon atoms and preferably from 6 to 9 carbon atoms.
• PPA may be more particularly a polyterephthalamide, ie a PPA in which terephthalic acid is used.
• the PPA is obtained by the copolymerization of terephthalic acid, isophthalic acid, at least one dicarboxylic acid, preferably adipic acid, and at least one aliphatic diamine.
• PPPs marketed by SOLVY ADVANCED POLYMERS under the trade name AMODEL ® are used in the context of the present invention.
• the multilayer structure used for the manufacture of the gas pipes is formed of three or four successive layers, the layer 1, the optional layer 2, the layer 3 and the layer 5, the layer 5 being in contact with the gas conveyed by the pipe.
• Layers 1 to 3 are the layers 1, the optional layer 2, the layer 3 and the layer 5, the layer 5 being in contact with the gas conveyed by the pipe.
• Layer 5 is a polyamide-based layer.
• the layer 5 may in particular comprise at least one polyamide, the polyamide being chosen from PA 11, PA 12 and an aliphatic polyamide resulting from the condensation of an aliphatic diamine having from 6 to 18 carbon atoms and an aliphatic diacid having from 9 to 18 carbon atoms.
• the layer 5 may furthermore comprise a functionalized polyolefin and / or a non-functionalized polyolefin. Reference will be made to the description of the functionalized polyolefins.
• Layer 5 may also comprise one or more additives, in particular those already mentioned previously for layer 1.
• the polyamide-based composition of layer 5 is identical to that described above for the composition of layer 1.
• the multilayer structure used for the manufacture of the gas pipes is formed of three, four or five successive layers, the layer 1, the optional layer 2, the layer
• composition of each of layers 1 to 3 is identical to that described above for the first aspect of the invention.
• layer 4 is optional.
• This layer 4 is a layer of binder interposed between the layers 3 and 5 to allow or optimize the adhesion of these layers 3 and 5 between them, and thus avoid any delamination phenomenon.
• the polyamide-based composition of layer 5 is identical to that described above for the composition of layer 1.
• the compositions of layers 2 and 4, on the one hand, and layers 1 and 5, on the other hand, of the same multilayer structure are identical.
• the multilayer structure used in the context of the present invention may further comprise a protective layer V, disposed on the layer 1.
• This protection layer V may be a heat-protection layer, a fire-resistant layer, an abrasion-resistant layer, an oxidation resistant layer, or a layer having simultaneously several of these properties.
• the multilayer structure described above is advantageously shaped so as to be in the form of a hollow body, preferably in the form of a tube or pipe.
• the tubes are manufactured by the coextrusion technique, hence the need to have a perfect adhesion between the different coextruded layers forming the structure.
• the multilayer structure is a tube
• this tube can be shaped so as to obtain a smooth tube or, on the contrary, a corrugated tube.
• the present invention will now be illustrated by various examples for which methane permeability has been measured at 23 ° C.
• the products implemented are the following:
• PA11 PA11 reference Besn TL - PA11 p: PA11 reference Besno P40 TL supplemented with a plasticizer
• Platamid®1 (50%) and Platamid®2 (50%), Platamid®1 being a 6/12 copolyamide (40/60) and Platamid®2 being a 6/12 copolyamide (70/30)
• reference HX 2560T - Orgalloy mixture of predominant PA 6, high density polyethylene and a compatibilizer containing a reference anhydride functionality 18501 N, this mixture bearing the reference LE60THM. All of the products listed above are marketed by ARKEMA FRANCE.
• PA11 p / binder / Orgalloy (450/100/450) PA11 / binder / Orgalloy / binder / PA11 (400/50/100/50/400) PA11 p / binder / Orgalloy / binder / PA11 p (400/50/100 / 50/400) PA11 / binder / EVOH / binder / PA11 (400/50/100/50/400) PA11 p / binder / EVOH / binder / PA11 p (400/50/100/50/400)

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• Engineering & Computer Science (AREA)
• General Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Rigid Pipes And Flexible Pipes (AREA)

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• 2006
  • 2006-11-30 FR FR0655218A patent/FR2909433B1/fr active Active
• 2007
  • 2007-11-26 EP EP20070858735 patent/EP2094481B1/fr not_active Revoked
  • 2007-11-26 RU RU2009124911/05A patent/RU2009124911A/ru not_active Application Discontinuation
  • 2007-11-26 JP JP2009538752A patent/JP5160557B2/ja not_active Expired - Fee Related
  • 2007-11-26 AT AT07858735T patent/ATE531513T1/de active
  • 2007-11-26 PL PL07858735T patent/PL2094481T3/pl unknown
  • 2007-11-26 KR KR1020097010738A patent/KR101249101B1/ko not_active IP Right Cessation
  • 2007-11-26 CN CNA2007800479283A patent/CN101600565A/zh active Pending
  • 2007-11-26 US US12/516,708 patent/US20100136274A1/en not_active Abandoned
  • 2007-11-26 ES ES07858735T patent/ES2376920T3/es active Active
  • 2007-11-26 WO PCT/FR2007/052395 patent/WO2008065300A1/fr active Application Filing
• 2013
  • 2013-05-02 US US13/875,898 patent/US8784526B2/en not_active Expired - Fee Related

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